Solvent dipole modulation of conduction band edge shift and charge recombination in robust dye-sensitized solar cells

Molecular modification is certified as a powerful strategy to adjust the energy alignment and electron transfer dynamics of dye-sensitized solar cells (DSCs). Herein, devices are assembled with three robust solvent (3-methoxypropionitrile, N,N-dimethylformamide and γ-butyrolactone) based electrolytes to elucidate the solvent dipole effects at the semiconductor-dye-electrolyte interface. Photovoltaic results demonstrate that open-circuit photovoltages of the devices vary linearly with the dipole moment of the solvents, along with an adverse dependence of the short-circuit photocurrent density under simulated irradiation. Impedance analysis reveals an apparent dipole moment-modulated conduction band edge shift of the nanocrystalline TiO(2) electrodes with respect to the redox potential of the electrolyte. Furthermore, the adverse shifts of the short-circuit photocurrent are explained by a dipole dependence of the driving force for electron injection and the interfacial charge recombination, together with a notably changed charge collection efficiency. Therefore, this study draws attention to the feasibility of tuning the electron transfer dynamics and energy alignment in photoelectrochemical devices by judiciously selecting the electrolyte solvents for further efficiency improvement, especially for those alternative organic sensitizers or quantum dots with inadequate electron injection driven forces.